Table 2 Synthesis of phenanthrolines 10–17a
route lies on a Povarov/oxidation sequence from simple chemicals
(1,2-phenylenediamines, aldehydes and ethyl vinyl ether), in TFE
or HFIP as promoting medium. As a perspective, this method
could be used with functionalised and/or enantiopure aldehydes
to obtain chiral phenanthrolines.
The Indo-French program CEFIPRA/IFCPAR (Project 3705-
1) is thanked for the PhD grant to KD. Central Glass Co. Ltd is
acknowledged for kind gift of HFIP.
Entry
1
Substrate
Product
Yield (%)
49
Notes and references
8-Aminoquinoline
¶ Some phen derivatives have specific names and acronyms. 4,7-
Diphenyl-1,10-phenanthroline: bathophenanthroline (bp); 2,9-dimethyl-
1,10-phenanthroline: neocuproine (neo); 2,9-dimethyl-4,7-diphenyl-1,10-
phenanthroline: bathocuproine (bc).
2b
8-Aminoquinoline
43
40
1 For reviews, see: (a) C. R. Luman and F. N. Castellano, in Compre-
hensive Coordination Chemistry II (ed.: J. M. McCleverty, T. J. Meyer),
vol. 1: Fundamentals: Ligands, Complexes, Synthesis, Purification, and
Structure (Ed.: A. B. P. Lever) Elsevier, 2008, p. 25; (b) P. G. Sammes
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2 For reviews, see: (a) E. Schoffers, Eur. J. Org. Chem., 2003, 1145; (b) G.
Chelucci and R. P. Thummel, Chem. Rev., 2002, 102, 3129.
3
4
3 For some selected examples of various phens as ligands in catalysis, see:
phen (a) L. J. Goossen, F. Manjolinho, B. A. Khan and N. Rodr´ıguez,
J. Org. Chem., 2009, 74, 2620; (b) F. Shibahara, E. Yamaguchi and T.
Murai, Chem. Commun., 2010, 46, 2471bp; (c) F. Valle´e, J. J. Mousseau
and A. B. Charrette, J. Am. Chem. Soc., 2010, 132, 1514; (d) Z. Li,
D. A. Capretto, R. Rahaman and C. He, Angew. Chem., Int. Ed., 2007,
46, 51843,4,7,8-Me4-phen; (e) R. A. Altman, A. Shafir, A. Choi, P. A.
Lichtor and S. L. Buchwald, J. Org. Chem., 2008, 73, 284neo; (f) J.
4
5
33
˚
Lindh, P.-A. Enquist, A. Pilotti, P. Nilsson and M. Larhed, J. Org.
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4 (a) J. E. Reed, S. Neidle and R. Vilar, Chem. Commun., 2007, 4366;
(b) C.-C. Cheng, Y.-N. Kuo, K.-S. Chuang, C.-F. Luo and W. J. Wang,
Angew. Chem., Int. Ed., 1999, 38, 1255.
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Chem. Soc., 1993, 115, 6699; (c) R. M. Everly, R. Ziessel, J. Suffert and
D. R. McMillin, Inorg. Chem., 1991, 30, 559.
5
6
6
7
42
50
6 C. O. Dietrich-Buchecker, P. A. Marnot and J.-P. Sauvage, Tetrahedron
Lett., 1982, 23, 5291.
7 E. C. Riesgo, X. Jin and R. P. Thummel, J. Org. Chem., 1996, 61, 3017.
8 F. H. Case and R. Sasin, J. Org. Chem., 1955, 20, 1330.
9 See also: G. Chelucci, D. Addis and S. Baldino, Tetrahedron Lett., 2007,
48, 3359.
10 (a) P. Belser, S. Bernhard and U. Guerig, Tetrahedron, 1996, 52, 2937;
(b) K. Madeja, J. Prakt. Chem., 1962, 17, 97.
11 (a) L. S. Povarov and B. M. Mikhailov, Izv. Akad. Nauk SSR Ser. Khim.,
1963, 953; For reviews, see: (b) D. Bello, R. Ramo´n and R. Lavilla, Curr.
Org. Chem., 2010, 14, 332; (c) V. V. Kouznetsov, Tetrahedron, 2009, 65,
2721; (d) P. Buonora, J.-C. Olsenb and T. Oh, Tetrahedron, 2001, 57,
6099.
7
8
9
44
40
8b
12 For some selected examples of the Povarov reaction, see: (a) E. Vicente-
Garc´ıa, F. Catti, R. Ramo´n and R. Lavilla, Org. Lett., 2010, 12, 860;
(b) F. Palacios, C. Alonso, A. Arrieta, F. P. Coss´ıo, J. M. Ezpeleta,
M. Fuertes and G. Rubiales, Eur. J. Org. Chem., 2010, 2091; (c) H.
Liu, G. Dagousset, G. Masson, P. Retailleau and J. Zhu, J. Am. Chem.
Soc., 2009, 131, 4598; (d) N. Shindoh, H. Tokuyama, Y. Takemoto
and K. Takasu, J. Org. Chem., 2008, 73, 7451; (e) T. Akiyama, H.
Morita and K. Fuchibe, J. Am. Chem. Soc., 2006, 128, 13070; (f) B.
Crousse, J.-P. Be´gue´ and D. Bonnet-Delpon, J. Org. Chem., 2000, 65,
5009.
a Reaction conditions: Povarov reaction: 8-aminoquinoline (0.5 mmol),
aldehyde (0.55 mmol), EVE (1.5 mmol) in TFE (1 mL), then oxidation:
aq. HCl 6 N (0.2 mL) under O2 atm. in MeCN (0.5 mL). b No aldehyde
was used, EVE (5 mmol) in HFIP (1 mL) then oxidation.
13 For reviews on fluoroalcohols, see: (a) I. A. Shuklov, N. V. Dubrovina
and A. Bo¨rner, Synthesis, 2007, 2925; (b) J.-P. Be´gue´, D. Bonnet-Delpon
and B. Crousse, Synlett, 2004, 18; (c) J.-P. Be´gue´, D. Bonnet-Delpon
and B. Crousse, in Handbook of Fluorous Chemistry (Eds: J. A. Gladysz,
D. P. Curran, I. T. Horvath), Wiley-VCH, Weinheim, 2004, p. 341.
In conclusion, we have developed an original methodology
to access to the metal ligands 8-aminoquinolines and phenan-
throlines with substituent(s) in a of the nitrogen atom(s). This
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